Observations on the boundary between zeolite facies and prehnite-pumpellyite facies

Using graphical analysis of the system CaO-Al₂O₃-SiO₂-H₂O-CO₂, this paper derives a topology relating the minerals calcite, laumontite, wairakite, prehnite, quartz, and zoisite. Simple thermodynamic reasoning allows this system to be applied to natural rocks and indicates that the first appearance of the assemblage epidote-chlorite-quartz (±albite) should mark the upper boundary of zeolite facies. This assemblage forms at the expense of laumontite+prehnite, laumontite+calcite, or laumontite+pumpellyite, with wairakite likely to replace laumontite as the stable zeolite at low pressures. In natural systems this proposed facies boundary is multivariant and, hence, it is likely to be strongly sensitive to compositional variables. For example, Na-bearing wairakite will be more stable than pure Ca-wairakite and increasing abundance of Fe³⁺ will tend to stabilize epidote+quartz at the expense of the zeolites. Because of this, monitoring the composition of minerals such as epidote, prehnite, or wairakite from lowvariance assemblages may provide a more-sensitive indicator of metamorphic grade than the presence or absence of any particular mineral assemblage.     

P--T Stabilities of Laumontite, Wairakite, Lawsonite, and Related Minerals in the System CaAl2Si2O8-SiO2-H2O

Hydrothermal investigation of the bulk composition CaO.Al₂O₃.4SiO₂+excessH₂O has been conducted using conventional techniques over thetemperature ranges 200–450 °C and 500–6000 barsP_fluid. A number of reactions have been studied by employingmineral mixtures consisting of reactants and products in about9: 1 and 1: 9 ratios. The phase relations were deduced fromrelatively long experiments by observing which seeded assemblagedisappeared or decreased markedly in one of the paired run charges. Laumontite was synthesized in the laboratory, probably for thefirst time. Laumontite was grown from seeded wairakite to over99 per cent using a weak NaCl solution. The refractive indicesof the synthetic material are about = 1.504 and = 1.514. Theaverage unit cell dimensions are a₀ = 14.761±0.005 Å;b₀ = 13.077±0.005 Å; c₀ = 7.561±0.003 Å;and ß = 112.02°±0.04°. Within the errorof measurement, the optical properties and cell parameters arein good agreement with those of natural laumontite. The equilibriumdehydration of laumontite involves two reactions: (1) laumontite= wairakite+2H₂O, passing through about 230 °C at 0.5 kb,255±5 °C at 1 kb, 282±5 °C at 2 kb, 297±5°C at 3 kb and 325±5 °C at 6 kb; and (2) laumontite= lawsonite+2 quartz+2H₂O, taking place at about 210 °Cat 3 kb and 275 °C at 3.2 kb. Above 300 °C, the equilibriumcurve for the solid-solid reaction (3) lawsonite+2 quartz =wairakite passes through 305 °C, 3.4 kb and 390 °C,4.4 kb. Equilibrium has been demonstrated unambiguously forthe above three reactions. The hydrothermal decomposition ofnatural laumontite above its own stability limit appears tobe a very slow process. Combined with previously published equilibria determined hydrothermallyfor wairakite, the phase relations are further investigatedby chemographic analysis interrelating the phases, laumontite,wairakite, lawsonite, anorthite, prehnite+kaolinite, and 2 pumpellyite+kaolinitein the system CaAl₂Si₂O₈-SiO₂-H₂O. This synthesis allowed theconstruction of a semiquantitative petrogenetic grid applicableto natural parageneses and the delineation of the physical conditionsfor the various low-grade metamorphic facies in low µCO₂environments. The similar stratigraphic zonations, consistentlyfound in a variety of environments, are recognized to be a functionof burial depth, geothermal gradient, and mineralogical andchemical composition of the parental rocks. Departures fromthe normal sequences are believed to be due to the combinationsof mineralogical variations, availability of H₂O, differencesin the ratio µCO₂/µH₂O, and the rate of reaction.The possible P-T boundaries for diagenesis, the zeolite facies,the lawsonite-albite facies, the prehnite-pumpellyite facies,and the adjacent metamorphic facies are illustrated diagrammatically.     

The thermodynamic properties and phase relations of some minerals in the system CaO-AI2O3-SiO2-H2O

The heat capacities of lawsonite, margante, prehnite and zoisite have been measured from 5 to 350 K with an adiabatic-shield calorimeter and from 320 to 999.9 K with a differential-scanning calorimeter. At 298.15 K, their heat capacities, corrected to end-member compositions, are 66.35, 77.30, 79.13 and 83.84 cal K^?1 mol^?1; their entropies are 54.98, 63.01, 69.97 and 70.71 cal K^?1 mol^?1, respectively. Their high-temperature heat capacities are described by the following equations (in calories, K, mol): Lawsonite (298–600 K): Cp° = 66.28 + 55.95 × 10^?3T ? 15.27 × 10⁵T^?2 Margarite (298–1000 K): Cp° = 101.83 + 24.17 × 10^?3T ? 30.24 × 10⁵T^?2 Prehnite (298–800 K): Cp° = 97.04 + 29.99 × 10^?3T ? 25.02 × 10⁵T^?2 Zoisite (298–730 K): Cp° = 98.92 + 36.36 × 10^?3T ? 24.08 × 10⁵T^?2 Calculated Clapeyron slopes for univariant equilibria in the CaO-Al₂O₃-SiO₂-H₂O system compare well with experimental results in most cases. However, the reaction zoisite + quartz = anorthite + grossular + H₂O and some reactions involving prehnite or margarite show disagreements between the experimentally determined and the calculated slopes which may possibly be due to disorder in experimental run products. A phase diagram, calculated from the measured thermodynamic values in conjunction with selected experimental results places strict limits on the stabilities of prehnite and assemblages such as prehnite + aragonite, grossular + lawsonite, grossular + quartz, zoisite + quartz, and zoisite + kyanite + quartz. The presence of this last assemblage in eclogites indicates that they were formed at moderate to high water pressure.     

Relationship between fluid-bearing and fluid-absent invariant points and a petrogenetic grid for a greenschist facies assemblage in the system CaO-MgO-Al2O3-SiO2-CO2-H2O

In the 6 component system CaO-MgO-Al₂O₃-SiO₂-CO₂-H₂ with 9 solid phases (quartz, plagioclase, epidote, tremolite, talc, chlorite, magnesite, calcite, dolomite) and a fluid phase, all 17 possible fluid-absent reactions have been set up and balanced. Using molar entropy and volume data for the solid phases, these reactions are arranged in P-T space about the 8 possible fluid-absent invariant points after the method of Schreinemakers. Field observations in Ordovician greenschist facies basic volcanics at Sofala N.S.W., indicate that neither talc+epidote nor magnesite+calcite are stable under the conditions of metamorphism. Assuming these conditions to apply to the theoretical study here, the fluid-absent invariant points are arranged in a relative fashion with fluid-absent reactions subdividing P-T space into smaller areas.A scheme which permits a fluid of composition (i.e. a fluid containing CO₂ and H₂O together with other components), is modeled by treating H₂O as a mobile component independent of CO₂, and by allowing values that lie off the locus of binary H₂O-CO₂. Taking into account that neither talc+epidote nor magnesite +calcite is to be permitted, the fluid scheme is used to set up and balance all 39 possible fluid-bearing reactions. These are then arranged about 20 valid fluid-bearing invariant points in space after the method of Korzhinskii and Sehreinemakers.A characteristic solid phase assemblage is defined for each P-T area using chemographic relations inherent from the fluid-absent boundary reactions. The fluid-bearing invariant points that have a solid assemblage compatible with the characteristic assemblage in a particular P-T area are stable within the P-T regime of that area. When these stable fluidbearing invariant points are arranged in a relative fashion in space, they outline a fluid grid which can be used to study the possible effects of local variation in X _fluid over the particular P-T regime.Symbols Used U chemical potential - S entropy - V molar volume - n coefficient of a phase in a reaction - X mole fraction - T temperature - P pressure - F number of degrees of freedom - C number of components - p number of phases - s solid - slope of reaction - 1 quartz - 2 plagioclase - 3 epidote - 4 tremolite - 5 talc - 6 chlorite - 7 dolomite - 8 magnesite - 9 calcite     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

Beginning of melting and subsolidus relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt.The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K₂O-CaO-Al₂O₃-SiO₂-H₂O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al₂O₃-SiO₂-H₂O.The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al₂O₃-SiO₂-H₂O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper.The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al₂SiO₅ polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

Phase equilibria among pumpellyite,lawsonite, epidote and associated minerals in low grade metamorphic rocks

Phase relations of pumpellyite, epidote, lawsonite, CaCO₃, paragonite, actinolite, crossite and iron oxide are analysed on an Al-Ca-Fe³⁺ diagram in which all minerals are projected from quartz, albite or Jadeite, chlorite and fluid. Fe²⁺ and Mg are treated as a single component because variation in Fe²⁺/Mg has little effect on the stability of phases on the diagram. Comparison of assemblages in the Franciscan, Shuksan, Sanbagawa, New Caledonia, Southern Italian, and Otago metamorphic terranes reveals several reactions, useful for construction of a petrogenetic grid:

1. lawsonite+crossite + paragonite = epidote+chlorite + albite + quartz + H₂O
2. lawsonite + crossite = pumpellyite + epidote + chlorite + albite+ quartz + H₂O
3. crossite + pumpellyite + quartz = epidote + actinolite + albite + chlorite + H₂O
4. crossite + epidote + quartz = actinolite + hematite + albite + chlorite + H₂O
5. calcite + epidote + chlorite + quartz = pumpellyite + actinolite + H₂O + CO₂
6. pumpellyite + chlorite + quartz = epidote + actinolite + H₂O

     

Prehnite-Pumpellyite to Greenschist Fades Transition in the Karmutsen Metabasites, Vancouver Island, B.C.

Mineral paragenescs in the prehnite-pumpellyite to greenschistfades transition of the Karmutsen metabasites are markedly differentbetween amygdule and matrix, indicating that the size of equilibriumdomain is very small. Characteristic amygdule assemblages (+chlorite + quartz) vary from: (1) prehnite + pumpeUyite + epidote,prehnite + pumpellyite + calcite, and pumpellyite + epidote+ calcite for the prehnite-pumpellyite facies; through (2) calcite+ epidote + prehnite or pumpellyite for the transition zone;to (3) actinolite + epidote + calrite for the greenschist facies.Actinolite first appears in the matrix of the transition zone.Na-rich wairakites containing rare analcime inclusions coexistwith epidote or Al-rich pumpellyite in one prehnite-pumpellyitefacies sample. Phase relations and compositions of these wairakite-bearingassemblages further suggest that pumpellyite may have a compositionalgap between 0.10 and 0.15 X_Fe?. Although the facies boundaries are gradational due to the multi-varianceof the assemblages, several transition equilibria are establishedin the amygdule assemblages. At low X_co2, pumpellyite disappearsprior to prehnite by a discontinuous-type reaction, pumpellyite+ quartz + CO₂ = prehnite + epidote + calcite + chlorite + H₂O,whereas prehnite disappears by a continuous-type reaction, prehnite+ CO₂ = calcite + epidote + quartz-l-H₂O. On the other hand,at higher X_CO2 a prehnite-out reaction, prehnite + chlorite+ H₂O + CO₂ = calcite + pumpellyite + quartz, precedes a pumpellyiteoutreaction, pumpellyite + CO₂ = calcite + epidote + chlorite +quartz + H₂O. The first appearance of the greenschist faciesassemblages is defined at both low and high XCOj by a reaction,calcite + chlorite + quartz = epidote + actinolite+ H₂O + CO₂.Thus, these transition equilibria are highly dependent on bothX_Fe³⁺ + of Ca-Al silicates and X_H20 of the fluid phase. Phaseequilibria together with the compositional data of Ca-Al silicatesindicate that the prehnite-pumpellyite to greenschist faciestransition for the Karmutsen metabasites occurred at approximately1.7 kb and 300?C, and at very low X_co2, probably far less than0.1.     

Experimentelle Untersuchung der Metamorphose von kieselig dolomitischen Sedimenten

During an experimental investigation of the metamorphism of siliceous dolomites the equilibrium data of the heterogeneous bivariant reaction 1 $$3{\text{ dolomite + 4 quartz + 1 H}}_{\text{2}} O \rightleftharpoons + 3 calcite + 3 CO_2 $$ were determined for the total fluid pressures of 1,000, 3,000 and 5,000 bars. The equilibrium conditions were found by experiments in which dolomite, quartz and water react to form talc, calcite and CO₂, as well as by experiments with reversible reaction direction. Results are shown on the temperature- \(X_{CO_2 } \) -diagram of Fig. 3. The temperature of formation of talc and calcite depends to a considerable extent on the composition of the CO₂-H₂O-gas phase; this can be read straight off the isobaric (P _f =const.) equilibrium curves in Fig. 3. In addition a strong dependence of the equilibrium temperature on the total pressure P _f was established (see Fig. 5). At a total gas pressure of 1,000 bars dolomite and quartz can react, according to the composition of the CO₂-H₂O-gas phase, to talc and calcite over the whole of the temperature range between about 350° and 490° C. This indicates that at low pressures the formation of talc and calcite takes place in the field of the albite-epidote-hornfels facies. At a pressure of 3,000 bars dolomite and quartz are stable up to about 550° C if the fluid phase is rich in carbon dioxide and correspondingly poor in water. Thus, this paragenesis can occur up to the stability field of staurolite [see annotation (5)] if the partial pressure of CO₂ is large. At the higher total gas pressure of 5,000 bars dolomite and quartz react even at medium CO₂-concentrations only at about 580° C to give talc and calcite. Therefore it is expected that in regional metamorphism at about 5,000 bars pressure or more the paragenesis dolomite plus quartz exists up to and within the stability field of staurolite and reacts only here to form talc and calcite after reaction (1) or tremolite and calcite after the following reaction (2)¹: $$5 dolomite + 8 quartz + 1 H_2 O \rightleftharpoons 1 tremolite + 3 calcite + 7 CO_2 $$ . The exact physico-chemical conditions under which dolomite, quartz and water react on the one hand to form talc, calcite and CO₂, and on the other hand to form tremolite, calcite and carbon dioxide, will be discussed later when our experimental investigations on the formation of tremolite are completed. First results were already published in a short note by Metz, Puhan and Winkler (1968).     

Fractionation of major elements between coexisting H2O-saturated silicate melt and silicate-saturated aqueous fluids in aluminosilicate systems at 1-2 GPa

From experimental data in the systems Na₂O-Al₂O₃-SiO₂-H₂O, K₂O-Al₂O₃-SiO₂-H₂O at 1100°C, and CaO-Al₂O₃-SiO₂-H₂O at 1200°C in the 1-2 GPa pressure range, the solution behavior of the individual oxides in coexisting H₂O-saturated silicate melts and silicate-saturated aqueous fluids appears to be incongruent. Recalculated on an anhydrous basis, in the CaO-Al₂O₃-SiO₂-H₂O system, CaO^fluid/CaO^melt < 1, whereas in the Na₂O-Al₂O₃-SiO₂-H₂O and K₂O-Al₂O₃-SiO₂-H₂O systems, K₂O^fluid/K₂O^melt and Na₂O^fluid/Na₂O^melt both are greater than 1. The aqueous fluids are depleted in alumina relative to silicate melt.In the Na₂O-Al₂O₃-SiO₂-H₂O, K₂O-Al₂O₃-SiO₂-H₂O, and CaO-Al₂O₃-SiO₂-H₂O systems, fluid/melt partition coefficients for the individual oxides range between ∼0.005 and 0.35 depending on oxide, bulk composition and pressure. The alkali partition coefficients are about an order of magnitude higher than that of CaO. Alumina and silica partition coefficient values in the CaO-Al₂O₃-SiO₂-H₂O system are 10-20% of the values for the same oxides in the Na₂O-Al₂O₃-SiO₂-H₂O and K₂O-Al₂O₃-SiO₂-H₂O systems.Positive correlations among individual partition coefficients and oxide concentrations in the aqueous fluids are consistent with complexing in the fluid that involves silicate polymers associated with alkalis and alkaline earths and aluminosilicate complexes where alkalis and alkaline earths may serve to charge-balance Al³⁺, which is, perhaps, in tetrahedral coordination. Alkali aluminosilicate complexes in aqueous fluid appear more stable than Ca-aluminosilicate complexes.     

Experimentelle Untersuchung der Reaktion Dolomit + Kalifeldspat + H2O ⇌ Phlogopit + Calcit + CO2

The equilibrium curve for the reaction 3 dolomite + 1 K-feldspar + 1 H₂O=1 phlogopite + 3 calcite + 3 CO₂ was determined experimentally at a total gas pressure of 2000 bars using two different methods.

1. In the first case water alone was added to the reactants. The CO₂ component of the gas phase was producted solely by the reaction under favourable P-T conditions. This manner of carrying out the reaction is called the “water method”. With this method sufficient time must be allowed for the gas phase to attain a constant composition (see Fig. 1). Reverse reactions were carried out using reaction products of the forward reaction.
2. In the second case silver oxalate + water were added to the reactants. Breakdown of the silver oxalate leads to formation of a CO₂-H₂O gasphase of definite composition. At constant temperature and gas pressure the \(X_{{\text{CO}}_{\text{2}} } \) determines whether the reaction products will be phlogopite + calcite or dolomite + K-feldspar. In this case it is not necessary to wait for equilibrium to be attained. This method is abbreviated the “oxalate method”. Reactants for reverse reactions are not identical with the products of the forward reaction.

At high temperatures the results of the two different methods agree well (see Tables 1 and 2). Equilibrium was attained in one case at 490° C and \(X_{{\text{CO}}_{\text{2}} } \) of approximately 0.77, and in the other case at 520° C and \(X_{{\text{CO}}_{\text{2}} } \) of 0.90. At lower temperatures there are considerable differences in the results. With the water method an \(X_{{\text{CO}}_{\text{2}} } \) of about 0.25 was reached at 450° C. With the oxalate method dolomite K-feldspar and water still react with each other at even higher \(X_{{\text{CO}}_{\text{2}} } \) values. Phlogopite, calcite and CO₂ are formed together with metastable talc. There are no criteria to indicate which of the methods is the correct one at lower temperatures and in Fig. 2, therefore, both equilibrium curves are plotted.     

Metamorphism of Calcareous Rocks in Three Roof Pendants in the Sierra Nevada, California

Two roof pendants in the Hope Valley area, Alpine County, containabundant calc-silicate assemblages which can be related to univariantor invariant equilibria in the CaO-Al₃O₃-SiO₂-H₂O-CO₂ system.Such assemblages are considered to represent components of reactionsthat buffered the chemistry of the pore fluid. Through dataobtained from microprobe analysis it is concluded that solidsolution in plagioclase, garnet, and clinozoisite are importantvariables such that on a TXco₂ projection each sample had aunique path during metamorphism. Differences in the plagioclasecomposition of nearby samples with assemblages related by thereaction: grossularite_(s.s)+quartz = anorthite_(s.s.)+wollastonite, suggest unique equilibration temperatures for assemblages inlocal domains. In the Twin Lakes pendant in Fresno County, thereaction: clinohumite+calcite+CO₂= 4forsterite+dolomite+H₂O, is importantin magnesian marbles. Contrasting parageneses, which are relatedby this equilibrium, are considered to reflect variations influid composition. Constrasting assemblages in calc-silicaterocks, which are linked by the reactions: calcite+quartz= wollastonite+CO₂, tremolite+calcite= dolomite+diopside+CO₂+H₂O, exist down to the scale of a thin section. Variation in Ti contentof idocrase may be an important factor in assemblages linkedby reactions involving this phase. This study suggests that during contact metamorphism of calcareousrocks in the Sierra Nevada, H₂O and CO₂ behaved as ‘initialvalue components’ (Zen, 1963) whose activities were controlledby reactions withion local systems.     

Synthesis and stability relations of wairakite,CaAl2 Si4 O12·2H2O

Hydrothermal investigation of the bulk composition CaO·Al₂O₃·4SiO₂ + excess H₂O has been conducted using conventional techniques over the temperature range 200–500° C and 500–5,000 bars P _fluid. The fully ordered wairakite was synthesized unequivocally in the laboratory, probably for the first time.The gradual, sluggish and continuous transformation from disordered to ordered wairakite evidently accounts for failure by previous investigators to synthesize ordered wairakite in runs of week-long duration. The dehydration of metastable disordered wairakite to metastable hexagonal anorthite, quartz and H₂O has been determined; this reaction takes place at temperatures exceeding 400° C, even at fluid pressures of 500 bars or less. The upper P _fluid-T boundary of the disordered phase is equivalent to the maximum temperature curve of synthetic wairakite presented by previous investigators. The hydrothermal breakdown of natural wairakite above its stability limit appears to be a very slow process.The equilibrium dehydration of wairakite to anorthite, quartz and H₂O occurs at 330±5° C at 500 bars, 348±5° C at 1,000 bars, 372±5° C at 2,000 bars and 385±5° C at 3,000 bars. Where fluid pressure equals total pressure, the thermal stability range of wairakite is about 100° C wide. At lower temperatures wairakite reacts with H₂O to form laumontite. Reconnaissance experiments dealing with the effect of CO₂ on stabilities of calcium zeolites suggest that wairakite or laumontite may be replaced by the assemblage calcite + montmorillonite in the presence of a CO₂-bearing fluid phase.The determined P _fluid -T field of wairakite is compatible with field observations in some metamorphic terrains where it is related to the shallow emplacement of granitic magma and with direct pressure-temperature measurements in certain active geothermal areas. Under inferred conditions of higher _CO2/_H2O ratios, essentially unmetamorphosed rocks grade directly into those characteristic of the greenschist facies; moderately high values of _CO2 in carbonate-bearing rocks result in the downgrade extension of the greenschist facies at the expense of zeolite-bearing assemblages.     

A model for phase equilibria in the prehnite-pumpellyite facies

Using the method of Schreinemakers, along with other thermodynamic considerations, a phase diagram for the system CaO-MgO-Al₂O₃-SiO₂-CO₂-H₂O was constructed. The phases prehnite, pumpellyite, calcite, chlorite, dolomite, quartz, tremolite, talc, zoisite, grossularite and vapor were considered in this construction. The results indicate that prehnite-pumpellyite facies mineral assemblages will only exist in equilibrium with a vapor phase in which the mole fraction of CO₂ is less than 0.2 at 1 kb, and less than 0.15 at 2 kb. Although talc could theoretically be a stable phase under these conditions, its common absence from rocks of this facies probably results from the existence of an enantiomorphic point which makes tremolite-calcite-CO₂ the stable assemblage at low X _{CO 2}, and the compositionally equivalent talc-calcite-CO₂ assemblage stable at moderate X _{CO 2}.     

Experimental determination of the reaction paragonite=jadeite+kyanite+H2O,and internally consistent thermodynamic data for part of the system Na2O−Al2O3−SiO2−H2O,with applications to eclogites and blueschists

Hydrothermal reversal experiments have been performed on the upper pressure stability of paragonite in the temperature range 550–740 ° C. The reaction $$\begin{gathered} {\text{NaAl}}_{\text{3}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{1 0}}} ({\text{OH)}}_{\text{2}} \hfill \\ {\text{ paragonite}} \hfill \\ {\text{ = NaAlSi}}_{\text{2}} {\text{O}}_{\text{6}} + {\text{Al}}_{\text{2}} {\text{SiO}}_{\text{5}} + {\text{H}}_{\text{2}} {\text{O}} \hfill \\ {\text{ jadeite kyanite vapour}} \hfill \\ \end{gathered}$$ has been bracketed at 550 ° C, 600 ° C, 650 ° C, and 700 ° C, at pressures 24–26 kb, 24–25.5 kb, 24–25 kb, and 23–24.5 kb respectively. The reaction has a shallow negative slope (? 10 bar °C^?1) and is of geobarometric significance to the stability of the eclogite assemblage, omphacite+kyanite. The experimental brackets are thermodynamically consistent with the lower pressure reversals of Chatterjee (1970, 1972), and a set of thermodynamic data is presented which satisfies all the reversal brackets for six reactions in the system Na₂O-Al₂O₃-SiO₂-H₂O. The Modified Redlich Kwong equation for H₂O (Holloway, 1977) predicts fugacities which are too high to satisfy the reversals of this study. The P-T stabilities of important eclogite and blueschist assemblages involving omphacite, kyanite, lawsonite, Jadeite, albite, chloritoid, and almandine with paragonite have been calculated using thermodynamic data derived from this study.     

Phase relations in the greenschist-blueschist-amphibolite-eclogite facies in the system Na2O-CaO-FeO-MgO-Al2O3-SiO2-H2O (NCFMASH), with application to metamorphic rocks from Samos, Greece

Calculated phase equilibria among the minerals sodic amphibole, calcic amphibole, garnet, chloritoid, talc, chlorite, paragonite, margarite, omphacite, plagioclase, carpholite, zoisite/clinozoisite, lawsonite, pyrophyllite, kyanite, sillimanite, quartz and H₂O are presented for the model system Na₂O-CaO-FeO-MgO-Al₂O₃-SiO₂-H₂O (NCFMASH), which is relevant for many greenschist, blueschist, amphibolite and eclogite facies rocks. Using the activity-composition relationships for multicomponent amphiboles constrained by Will and Powell (1992), equilibria containing coexisting calcic and sodic amphiboles could be determined. The blueschist–greenschist transition reaction in the NCFMASH system, for example, is defined by the univariant reaction sodic amphibole + zoisite = calcic amphibole + chlorite + paragonite + plagioclase (+ quartz + H₂O) occurring between approximately 420 and 450 °C at 9.5 to 10 kbar. The calculated petrogenetic grid is a valuable tool for reconstructing the PT-evolution of metabasic rocks. This is shown for rocks from the island of Samos, Greece. On the basis of mineral and whole rock analyses, PT-pseudosections were calculated and, together with the observed mineral assemblages and reaction textures, are used to reconstruct PT-paths. For rocks from northern Samos, pseudomorphs after lawsonite preserved in garnet, the assemblage sodic amphibole-garnet-paragonite-chlorite-zoisite-quartz and the retrograde appearance of albitic plagioclase and the formation of calcic amphibole around sodic amphibole constrain a clockwise PT-path that reaches its thermal maximum at some 520 °C and 19 kbar. The derived PT-trajectory indicates cooling during exhumation of the rocks and is similar to paths for rocks from the western part of the Attic-Cycladic crystalline complex. Rocks from eastern Samos indicate lower pressures and are probably related to high-pressure rocks from the Menderes Massif in western Turkey. Received: 8 July 1997 / Accepted: 11 February 1998     

Antigorite-ophicarbonates: Phase relations in a portion of the system CaO-MgO-SiO2-H2O-CO2

The occurrence of critical assemblages among antigorite, diopside, tremolite, forsterite, talc, calcite, dolomite and magnesite in progressively metamorphosed ophicarbonate rocks, together with experimental data, permits the construction of phase diagrams in terms of the variables P, T, and composition of a binary CO₂-H₂O fluid. Equilibrium constants are given for the 30 equilibria that describe all relations among the above phases. Ophicalcite, ophidolomite, and ophimagnesite assemblages occupy partially overlapping fields in the diagram. The upper temperature limit of ophicalcite rocks lies below that of ophidolomite and ophimagnesite. The fluid phase in ophicarbonate rocks has 0.8$$ " align="middle" border="0"> , and there are indications that during their progressive metamorphism is approximately equal to P _total.     

The pressure and temperature stability limits of lawsonite: implications for H2O recycling in subduction zones

The stability relations of lawsonite, CaAl₂Si₂O₇(OH)₂H₂O, have been investigated at pressures of 6 to 14 GPa and temperatures of 740 to 1150°C in a multi-anvil apparatus. Experiments used the bulk composition lawsonite+H₂O to determine the maximum stability of lawsonite. Lawsonite is stable on its own bulk composition to a pressure of 13.5 GPa at 800°C, and between 6.5 and 12 GPa at 1000°C. Its composition does not change with pressure or temperature. All lawsonite reactions have grossular, vapour and two other phases in the system Al₂O₃-SiO₂-H₂O (ASH) on their high-temperature side. A Schreinemakers analysis of the ASH phases was used to relate the reactions to each other. At the lowest pressures studied lawsonite breaks down to grossular+kyanite+coesite+vapour in a reaction passing through 980°C at 6 GPa and 1070°C at 9 GPa. Above 9 GPa the reactions coesite=stishovite and kyanite+vapour=topaz-OH are crossed. The maximum thermal stability of lawsonite is at 1080°C, at 9.4 GPa. At higher pressures the lawsonite breakdown reactions have negative slopes. The reaction lawsonite=grossular+topaz-OH+stishovite+vapour passes through 1070°C at 10 GPa and 1010°C at 12 GPa. At 14 GPa, 740–840°C, lawsonite is unstable relative to the assemblage grossular+diaspore+vapour+a hydrous phase with an Al:Si ratio of 1:1. Oxide totals in electron microprobe analyses suggest that the composition of this phase is AlSiO₃(OH). Two experiments on the bulk composition lawsonite+pyrope [Mg₃Al₂Si₃O₁₂] show that at 10 GPa the reaction lawsonite=Gr-Py_ss+topaz-OH+stishovite+vapour is displaced down temperature from the end-member reaction by 200°C for a garnet composition of Gr₂₀Py₈₀. Calculations suggest similar temperature displacements for reaction between lawsonite and Gr-Py-Alm garnets of compositions likely to occur in high-pressure eclogites. Temperatures in subduction zones remain relatively low to considerable depth, and therefore slab P-T paths can be within the stability field of lawsonite from the conditions of its crystallisation in blueschists and eclogites, up to pressures of at least 10 GPa. Lawsonite contains 11.5 wt% H₂O, which when released may trigger partial melting of the slab or mantle, or be incorporated in hydrous phases such as the aluminosilicates synthesised here. These phases may then transport H₂O to an even greater depth in the mantle.     

Experimental investigation of the mechanism of the reaction: 1 tremolite+11 dolomite ⇌ 8 forsterite+13 calcite+9 CO2+1H2O

Stoichiometric mixtures of tremolite and dolomite were heated to 50° C above equilibrium temperatures to form forsterite and calcite. The pressure of the CO₂-H₂O fluid was 5 Kb and \(X_{{\text{CO}}_{\text{2}} }\) varied from 0.1 to 0.6. The extent of the conversion was determined by the amount of CO₂ produced. The resulting mixtures of unreacted tremolite and dolomite and of newly-formed forsterite and calcite were examined with a scanning electron microscope. All tremolite and dolomite grains showed obvious signs of dissolution. At fluid compositions with \(X_{{\text{CO}}_{\text{2}} }\) less than about 0.4, the forsterite and calcite crystals are randomly distributed throughout the charges, indicating that surfaces of the reactants are not a controlling factor with respect to the sites of nucleation of the products. A change is observed when \(X_{{\text{CO}}_{\text{2}} }\) is greater than about 0.4; the forsterite and calcite crystals now nucleate and grow at the surface of the dolomite grains, thus indicating a change in mechanism at medium CO₂ concentrations. As the reaction progresses, the dolomite grains become more and more surrounded by forsterite and calcite, finally forming armoured relics of dolomite. Under experimental conditions this characteristic texture can only be formed if the CO₂-concentration is greater than about 40 mole %. These findings make it possible to estimate the CO₂-concentration from the texture of the dolomite+tremolite+forsterite+calcite assemblage. The results suggest a dissolution-precipitation mechanism for the reaction investigated. In a simplified form it consists of the following 4 steps:

1. Dissolution of the reactants tremolite and dolomite.
2. Diffusion of the dissolved constituents in the fluid.
3. Heterogeneous nucleation of the product minerals.
4. Growth of forsterite and calcite from the fluid.

Two possible explanations are discussed for the development of the amoured texture at \(X_{{\text{CO}}_{\text{2}} }\) above 0.4. The first is based upon the assumption that dolomite has a lower rate of dissolution than tremolite at high \(X_{{\text{CO}}_{\text{2}} }\) values resulting in preferential calcite and forsterite nucleation and growth on the dolomite surface. An alternative explanation is the formation of a raised CO₂ concentration around the dolomite grains at high \(X_{{\text{CO}}_{\text{2}} }\) values, leading to product precipitation on the dolomite crystals.     

Experiments on the phase transition calcite+wollastonite+ +epidote=grossular-andraditess+CO2+H2O

The reaction 2 epidote+2 calcite+3 wollastonite3 grossular-andradite_ss+ 2 CO₂+1 H₂O has been explored by hydrothermal experiments at a total fluid pressure of 1000 bars. For a grossular-andradite_ss of andradite ₂₅ composition, the isobaric univariant curve passes through the points 458°C: X_CO2=0.00; 521°C: X_CO2=0.026; 523°C: X_CO2=0.052; 526°C: 0.088; 528°C: X_CO2=0.104. This curve intersects the isobaric univariant curve of the reaction calcite+quartz+[H₂O] wollastonite+CO₂+[H₂O] at the isobaric invariant point around 528°C and X_CO2=0.12. At higher values of X_CO2, this reaction is replaced by another one, namely: 2 epidote+5 calcite+3 quartz3 grossular-andradite_ss+5 CO₂+ 1 H₂O. It is demonstrated that both the reactions do actually take place during the metamorphism of calcareous rocks. The petrologic significance of contrasted sequence of reactions within this system observed by various workers is also discussed.